Steering the outcome of a photochemical reaction - an in silico experiment on the H2CSO sulfine using few-femtosecond dump pulses

Mignolet, Benoit; Curchod, Basile FE

Abstract

We propose a pump-dump control scheme using sub-10 fs pulses to enhance the photochemical formation of the three-membered C–S–O ring oxathiirane from the parent H2CSO sulfine molecule. The ultrashort nature of the pulses is essential to promptly alter the photoinduced dynamics, e.g., while a bond is elongating, which is key to selectively form the oxathiirane by radiative dumping. We carried out an in silico pump-dump experiment with excited-state dynamics simulations that include the interaction with electric field of the pump and dump pulses. By applying the dump pulse when the CS bond is elongating, the population transferred to the ground state will form the oxathiirane with a branching ratio of 4, much higher than the one solely due to nonradiative relaxation (0.66). The overall oxathiirane yield can be increased by up to 17% when the 6 fs IR dump pulse is applied at a delay time of 47 fs.

Citation

Mignolet, B., & Curchod, B. F. (2019). Steering the outcome of a photochemical reaction - an in silico experiment on the H2CSO sulfine using few-femtosecond dump pulses. The Journal of Chemical Physics, 150(10), Article 101101. https://doi.org/10.1063/1.5089124

• Journal Article Type: Article
• Acceptance Date: Feb 25, 2019
• Online Publication Date: Mar 12, 2019
• Publication Date: Mar 14, 2019
• Deposit Date: Feb 25, 2019
• Publicly Available Date: Mar 12, 2020
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 150
• Issue: 10
• Article Number: 101101
• DOI: https://doi.org/10.1063/1.5089124
• Public URL: https://durham-repository.worktribe.com/output/1307365